• Calculation of nondifferential properties for atomic ground states /

      Langfelder, Peter.; Department of Physics (Brock University, 1997-05-21)
      A new method for sampling the exact (within the nodal error) ground state distribution and nondiflPerential properties of multielectron systems is developed and applied to firstrow atoms. Calculated properties are the distribution moments and the electronic density at the nucleus (the 6 operator). For this purpose, new simple trial functions are developed and optimized. First, using Hydrogen as a test case, we demonstrate the accuracy of our algorithm and its sensitivity to error in the trial function. Applications to first row atoms are then described. We obtain results which are more satisfactory than the ones obtained previously using Monte Carlo methods, despite the relative crudeness of our trial functions. Also, a comparison is made with results of highly accurate post-Hartree Fock calculations, thereby illuminating the nodal error in our estimates. Taking into account the CPU time spent, our results, particularly for the 8 operator, have a relatively large variance. Several ways of improving the eflSciency together with some extensions of the algorithm are suggested.
    • Diffusion Monte Carlo study of electronic properties for H and Be atoms /

      Yu, Li.; Department of Physics (Brock University, 2006-06-04)
      We examined three different algorithms used in diffusion Monte Carlo (DMC) to study their precisions and accuracies in predicting properties of isolated atoms, which are H atom ground state, Be atom ground state and H atom first excited state. All three algorithms — basic DMC, minimal stochastic reconfiguration DMC, and pure DMC, each with future-walking, are successfully impletmented in ground state energy and simple moments calculations with satisfactory results. Pure diffusion Monte Carlo with future-walking algorithm is proven to be the simplest approach with the least variance. Polarizabilities for Be atom ground state and H atom first excited state are not satisfactorily estimated in the infinitesimal differentiation approach. Likewise, an approach using the finite field approximation with an unperturbed wavefunction for the latter system also fails. However, accurate estimations for the a-polarizabilities are obtained by using wavefunctions that come from the time-independent perturbation theory. This suggests the flaw in our approach to polarizability estimation for these difficult cases rests with our having assumed the trial function is unaffected by infinitesimal perturbations in the Hamiltonian.
    • Exact property estimation from diffusion Monte Carlo with minimal stochastic reconfiguration /

      Bosá, Ivana.; Department of Earth Sciences (Brock University, 2004-07-14)
      Our objective is to develop a diffusion Monte Carlo (DMC) algorithm to estimate the exact expectation values, ($o|^|^o), of multiplicative operators, such as polarizabilities and high-order hyperpolarizabilities, for isolated atoms and molecules. The existing forward-walking pure diffusion Monte Carlo (FW-PDMC) algorithm which attempts this has a serious bias. On the other hand, the DMC algorithm with minimal stochastic reconfiguration provides unbiased estimates of the energies, but the expectation values ($o|^|^) are contaminated by ^, an user specified, approximate wave function, when A does not commute with the Hamiltonian. We modified the latter algorithm to obtain the exact expectation values for these operators, while at the same time eliminating the bias. To compare the efficiency of FW-PDMC and the modified DMC algorithms we calculated simple properties of the H atom, such as various functions of coordinates and polarizabilities. Using three non-exact wave functions, one of moderate quality and the others very crude, in each case the results are within statistical error of the exact values.
    • Histogram filtering as a tool in variational Monte Carlo optimization

      Å najdr, Martin.; Department of Physics (Brock University, 1999-07-09)
      Optimization of wave functions in quantum Monte Carlo is a difficult task because the statistical uncertainty inherent to the technique makes the absolute determination of the global minimum difficult. To optimize these wave functions we generate a large number of possible minima using many independently generated Monte Carlo ensembles and perform a conjugate gradient optimization. Then we construct histograms of the resulting nominally optimal parameter sets and "filter" them to identify which parameter sets "go together" to generate a local minimum. We follow with correlated-sampling verification runs to find the global minimum. We illustrate this technique for variance and variational energy optimization for a variety of wave functions for small systellls. For such optimized wave functions we calculate the variational energy and variance as well as various non-differential properties. The optimizations are either on par with or superior to determinations in the literature. Furthermore, we show that this technique is sufficiently robust that for molecules one may determine the optimal geometry at tIle same time as one optimizes the variational energy.
    • Monte Carlo study of the XY-model on quasi-periodic lattices

      Reid, R. William.; Department of Physics (Brock University, 1996-07-09)
      Monte Carlo Simulations were carried out using a nearest neighbour ferromagnetic XYmodel, on both 2-D and 3-D quasi-periodic lattices. In the case of 2-D, both the unfrustrated and frustrated XV-model were studied. For the unfrustrated 2-D XV-model, we have examined the magnetization, specific heat, linear susceptibility, helicity modulus and the derivative of the helicity modulus with respect to inverse temperature. The behaviour of all these quatities point to a Kosterlitz-Thouless transition occuring in temperature range Te == (1.0 -1.05) JlkB and with critical exponents that are consistent with previous results (obtained for crystalline lattices) . However, in the frustrated case, analysis of the spin glass susceptibility and EdwardsAnderson order parameter, in addition to the magnetization, specific heat and linear susceptibility, support a spin glass transition. In the case where the 'thin' rhombus is fully frustrated, a freezing transition occurs at Tf == 0.137 JlkB , which contradicts previous work suggesting the critical dimension of spin glasses to be de > 2 . In the 3-D systems, examination of the magnetization, specific heat and linear susceptibility reveal a conventional second order phase transition. Through a cumulant analysis and finite size scaling, a critical temperature of Te == (2.292 ± 0.003) JI kB and critical exponents of 0:' == 0.03 ± 0.03, f3 == 0.30 ± 0.01 and I == 1.31 ± 0.02 have been obtained.
    • Optimization of the valence energy variance of the CuH molecule

      Belohorec, Peter.; Department of Physics (Brock University, 1992-07-09)
      We developed the concept of split-'t to deal with the large molecules (in terms of the number of electrons and nuclear charge Z). This naturally leads to partitioning the local energy into components due to each electron shell. The minimization of the variation of the valence shell local energy is used to optimize a simple two parameter CuH wave function. Molecular properties (spectroscopic constants and the dipole moment) are calculated for the optimized and nearly optimized wave functions using the Variational Quantum Monte Carlo method. Our best results are comparable to those from the single and double configuration interaction (SDCI) method.
    • Variational Monte Carlo estimation of the dissociation energy of CuH using correlated sampling

      Dobos, Andrej.; Department of Physics (Brock University, 1994-07-09)
      A new approach to treating large Z systems by quantum Monte Carlo has been developed. It naturally leads to notion of the 'valence energy'. Possibilities of the new approach has been explored by optimizing the wave function for CuH and Cu and computing dissociation energy and dipole moment of CuH using variational Monte Carlo. The dissociation energy obtained is about 40% smaller than the experimental value; the method is comparable with SCF and simple pseudopotential calculations. The dipole moment differs from the best theoretical estimate by about 50% what is again comparable with other methods (Complete Active Space SCF and pseudopotential methods).